Application of polyoxometallate as precipitation inducer for preparing ionic nano-enzyme catalyst and preparation method of ionic nano-enzyme catalyst
By using polymethoxylate as precipitation inducers, the problem of difficult to balance the precipitation effect and production cost in the preparation process of ionic nanoenzyme catalysts in the prior art is solved, and a rapid and economical preparation of nanoenzyme catalysts is achieved.
Patent Information
- Application Number
- CN202411994742.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-31
- Publication Date
- 2025-04-08
AI Technical Summary
The preparation process of existing ionic nanoenzyme catalysts cannot take into account the precipitation effect and production cost of nanoenzyme catalysts.
The polymethoxylate salt is used as the precipitation inducer for preparing the ionic nanoenzyme catalyst, and the reaction is carried out by mixing the polymethoxylate salt, the metal salt compound solution, the organic ligand solution and water to obtain the ionic nanoenzyme catalyst.
The rapid induction of metal ions and ligand precipitation in aqueous solution is achieved, providing a universal preparation method for ionic nanoenzyme catalysts, reducing production costs and significantly speeding up the precipitation process.
Smart Images
Figure CN119771504A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of nanozyme catalysts, and in particular to the use of a polyoxometalate as a precipitation inducer for preparing an ionic nanozyme catalyst and a method for preparing an ionic nanozyme catalyst. Background Art
[0002] Nanocatalysts and esterase-like catalysts are an important class of biocatalysts, widely used in food, medicine, papermaking and fine chemicals. The development of nanoenzyme catalysts aims to simulate the catalytic properties of natural enzymes to improve the efficiency of industrial production and the stability of catalysts. These catalysts are usually composed of metal ions and ligands, and the main binding effect is electrostatic force or coordination.
[0003] In the preparation process of ionic nanozyme catalysts, a key step is to precipitate them from aqueous solution, and the difficulty of this process actually depends on the solubility of the ionic nanozyme catalyst itself. In order to achieve this goal, it is usually necessary to find a suitable precipitant or poor solvent to induce the precipitation of metal compounds, and different ionic nanozyme catalysts also require different precipitants or poor solvents, which further increases the process and cost of screening precipitants or poor solvents, thereby greatly limiting the industrial production and application of ionic nanozyme catalysts.
[0004] Therefore, how to balance the precipitation effect and production cost of ionic nanozyme catalysts has become a technical problem that needs to be solved urgently. Summary of the invention
[0005] In view of this, the present invention provides an application of polyoxometalate as a precipitation inducer for preparing ionic nanozyme catalysts and a method for preparing ionic nanozyme catalysts, so as to solve the problem that the preparation process of existing ionic nanozyme catalysts cannot take into account both the precipitation effect and the production cost of the nanozyme catalysts.
[0006] In order to achieve the above object, the present invention adopts the following technical solution:
[0007] The present invention provides an application of a polyoxometalate as a precipitation inducer for preparing an ionic nanozyme catalyst.
[0008] The present invention also provides a method for preparing an ionic nanozyme catalyst, comprising the following steps:
[0009] The polyoxometalate, metal salt compound solution, organic ligand solution and water are mixed and reacted to obtain an ionic nanozyme catalyst.
[0010] Preferably, the polyoxometalate includes one or more of sodium phosphotungstate, sodium phosphomolybdate and ammonium heptamolybdate.
[0011] Preferably, the mass volume ratio of the polyoxometalate to water is 1-50 mg:1 mL.
[0012] Preferably, the reaction time is 1 to 60 minutes.
[0013] Preferably, the ionic nanozyme catalyst comprises one of Zn-carnosine, ZIF-8 and ZIF-67.
[0014] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:
[0015] 1. The present invention uses polyoxometalates as precipitation inducers for preparing ionic nanozyme catalysts, which can induce rapid precipitation of metal ions and ligands in aqueous solution, thereby providing a general method for preparing ionic nanozyme catalysts, avoiding the cumbersome screening process and cost of precipitants and poor solvents. At the same time, the preparation method of the present invention only requires a small amount of polyoxometalates to achieve rapid precipitation of metal ions and ligands, which is more conducive to reducing the production cost of nanozyme catalysts.
[0016] 2. The use of the polyoxometalate of the present invention as a precipitation inducer for preparing an ionic nanozyme catalyst can accelerate the precipitation process of the ionic nanozyme catalyst. The precipitation process of the existing ionic nanozyme catalyst takes a long time. For example, the existing precipitation process for preparing Zn-carnosine requires 5 hours, and the existing precipitation process for preparing ZIF-67 and ZIF-8 requires 24 hours. The preparation method of the general ionic nanozyme catalyst provided by the present invention only takes 1 to 60 minutes, and even a white precipitate can be observed after the polyoxometalate, metal salt compound solution, organic ligand solution and water are mixed, which greatly improves the precipitation effect of the nanozyme catalyst and reduces the precipitation time of the nanozyme catalyst. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.
[0018] Figure 1 This is a scanning electron microscope image of the Zn-carnosine nanozyme catalyst prepared in Example 1;
[0019] Figure 2 This is a diagram showing the results of the esterase-like catalytic activity verification of the Zn-carnosine nanozyme catalyst prepared in Example 1;
[0020] Figure 3 The X-ray diffraction spectra of the Zn-carnosine nanozyme catalysts prepared in Example 1 and Comparative Example 1. DETAILED DESCRIPTION
[0021] The present invention provides an application of a polyoxometalate as a precipitation inducer for preparing an ionic nanozyme catalyst.
[0022] The present invention also provides a method for preparing an ionic nanozyme catalyst, comprising the following steps:
[0023] The polyoxometalate, metal salt compound solution, organic ligand solution and water are mixed and reacted to obtain an ionic nanozyme catalyst.
[0024] In the present invention, the polyoxometalate includes one or more of sodium phosphotungstate, sodium phosphomolybdate and ammonium heptamolybdate.
[0025] In the present invention, the mass volume ratio of the polyoxometalate to water is 1-50 mg:1 mL, preferably 2-45 mg:1 mL, more preferably 5-40 mg:1 mL, and even more preferably 10-25 mg:1 mL.
[0026] In the present invention, the reaction time is 1 to 60 min, preferably 1.2 to 50 min, more preferably 1.5 to 20 min, and even more preferably 1.8 to 10 min.
[0027] In the present invention, the ionic nanozyme catalyst includes one of Zn-carnosine, ZIF-8 and ZIF-67.
[0028] In the present invention, the Zn-carnosine is Car-Zn MOFs.
[0029] In the present invention, the principle of the reaction is: polyoxometalate is a highly polar cluster with multiple negative charges. When it is dissolved in water together with metal ions, the electrostatic force will attract the metal ions to adsorb around the polyoxometalate, forming an ionic atmosphere with increased local concentration; therefore, after the ligand is added, the high local concentration will cause the metal-ligand to form a precipitate more quickly.
[0030] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.
[0031] Example 1 Preparation of Zn-carnosine nanozyme catalyst
[0032] 20 mg of sodium phosphotungstate was mixed with 1 mL of 160 mmol / L Zn(NO3)2·6H2O aqueous solution and 1 mL of deionized water, and 2 mL of 80 mmol / L L-carnosine aqueous solution was added. After reacting for 5 minutes, the mixture was centrifuged at 8000 r / min for 7 minutes and washed with deionized water three times to obtain a Zn-carnosine nanozyme catalyst, namely Zn-Car.
[0033] The Zn-carnosine nanozyme catalyst prepared in this example was scanned using a scanning electron microscope, and the scanning electron microscope image obtained was as follows: Figure 1 As shown, from Figure 1 It can be seen that the Zn-carnosine nanozyme catalyst obtained by the present invention is a nanoparticle with good dispersibility, and similar to the catalyst prepared by the traditional preparation method, has a lower particle size and high dispersibility;
[0034] The Zn-carnosine nanozyme catalyst prepared in this example was subjected to an esterase-like catalytic activity verification experiment, wherein the catalytic activity verification experiment used p-nitrophenol acetate as a substrate, and a group without adding a catalyst was used as a control group, and the esterase-like catalytic activity verification experiment was performed using the same steps as above. The results are as follows Figure 2 As shown by Figure 2 It can be seen that the red line is a control group without adding a catalyst, and the black line is an experimental group with the Zn-carnosine nanozyme catalyst prepared in this example. By comparison, it can be seen that the Zn-carnosine nanozyme catalyst prepared in the present invention has esterase-like activity and can catalyze the hydrolysis of p-nitrophenol acetate.
[0035] Example 2 Preparation of ZIF-67 Nanozyme Catalyst
[0036] 15 mg of sodium phosphotungstate was mixed with 15 mL of 30 mg / mL Co(NO3)2·6H2O aqueous solution, and 10 mL of 0.1 g / mL 2-methylimidazole aqueous solution was added. After reacting for 1 hour, the mixture was centrifuged at 8000 r / min for 5 minutes and washed three times with methanol to obtain a purple precipitate, namely ZIF-67.
[0037] Example 3 Preparation of ZIF-8 Nanozyme Catalyst
[0038] 15 mg of sodium phosphotungstate was mixed with 15 mL of a 30 mg / mL Zn(NO3)2·6H2O aqueous solution, and 10 mL of a 0.1 g / mL 2-methylimidazole aqueous solution was added. After reacting for 1 hour, the mixture was centrifuged at 8000 r / min for 5 minutes and washed three times with methanol to obtain a white precipitate, namely ZIF-8.
[0039] Comparative Example 1
[0040] 1 mL of Zn(NO3)2·6H2O with a molar concentration of 160 mmol / L and 2 mL of L-carnosine solution with a molar concentration of 80 mmol / L were mixed evenly, and then 4 mL of ethanol and 2 mL of water were added. After stirring for 5 minutes, the mixture was allowed to stand for 5 hours, and then centrifuged at a speed of 8000 r / min for 7 minutes, and then washed with deionized water for 3 times to obtain a Zn-carnosine nanozyme catalyst, namely Zn-Car (denoted as Zn-Car (without PW 12 )).
[0041] The Zn-carnosine nanozyme catalyst prepared in Example 1 and Comparative Example 1 was subjected to phase analysis, and the obtained X-ray diffraction spectrum was as follows: Figure 3 As shown, from Figure 3 It can be seen that the addition of sodium phosphotungstate causes Zn-carnosine to transform from crystalline to amorphous, which accelerates the precipitation of the material.
[0042] Comparative Example 2
[0043] 0.45 g of cobalt nitrate hexahydrate was mixed with 15 mL of water, and 10 mL of 0.1 g / mL 2-methylimidazole aqueous solution was added. After reacting for 24 hours, the mixture was centrifuged at 8000 r / min for 5 minutes and then washed three times with methanol to obtain a purple precipitate, namely ZIF-67.
[0044] Comparative Example 3
[0045] 0.45 g of zinc nitrate hexahydrate was mixed with 15 mL of water, and 10 mL of 0.1 g / mL 2-methylimidazole aqueous solution was added. After reacting for 24 hours, the mixture was centrifuged at 8000 r / min for 5 minutes and then washed with methanol three times to obtain a white precipitate, namely ZIF-8.
[0046] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. Application of polyoxometalates as precipitation inducers for the preparation of ionic nanozyme catalysts.
2. A method for preparing an ionic nanozyme catalyst, characterized in that: The steps include: The polyoxometalate, metal salt compound solution, organic ligand solution and water are mixed and reacted to obtain an ionic nanozyme catalyst.
3. The method for preparing an ionic nanozyme catalyst according to claim 2, characterized in that: The polyoxometalate includes one or more of sodium phosphotungstate, sodium phosphomolybdate and ammonium heptamolybdate.
4. The method for preparing an ionic nanozyme catalyst according to any one of claims 2 to 3, characterized in that: The mass volume ratio of the polyoxometalate to water is 1-50 mg:1 mL.
5. The method for preparing an ionic nanozyme catalyst according to claim 4, characterized in that: The reaction time is 1 to 60 minutes.
6. The method for preparing an ionic nanozyme catalyst according to claim 5, characterized in that: The ionic nanozyme catalyst includes one of Zn-carnosine, ZIF-8 and ZIF-67.